Pseudocapacitance is commonly associated with surface or near-surface reversible redox reactions, as observed with RuO2·xH2O in an acidic electrolyte. However, we recently demonstrated that a pseudocapacitive mechanism occurs when lithium ions are inserted into mesoporous and nanocrystal films of orthorhombic Nb2O5 (T-Nb2O5; refs 1,2). Here, we quantify the kinetics of charge storage in T-Nb2O5: currents that vary inversely with time, charge-storage capacity that is mostly independent of rate, and redox peaks that exhibit small voltage offsets even at high rates. We also define the structural characteristics necessary for this process, termed intercalation pseudocapacitance, which are a crystalline network that offers two-dimensional transport pathways and little structural change on intercalation. The principal benefit realized from intercalation pseudocapacitance is that high levels of charge storage are achieved within short periods of time because there are no limitations from solid-state diffusion. Thick electrodes (up to 40 μm thick) prepared with T-Nb2O5 offer the promise of exploiting intercalation pseudocapacitance to obtain high-rate charge-storage devices.

Electrochemical energy storage technology is based on devices capable of exhibiting high energy density (batteries) or high power density (electrochemical capacitors). There is a growing need, for current and near-future applications, where both high energy and high power densities are required in the same material. Pseudocapacitance, a faradaic process involving surface or near surface redox reactions, offers a means of achieving high energy density at high charge-discharge rates. Here, we focus on the pseudocapacitive properties of transition metal oxides. First, we introduce pseudocapacitance and describe its electrochemical features. Then, we review the most relevant pseudocapacitive materials in aqueous and non-aqueous electrolytes. The major challenges for pseudocapacitive materials along with a future outlook are detailed at the end. Broader context The importance of electrical energy storage will continue to grow as markets for consumer electronics and electrication of transportation expand and energy storage systems for renewable energy sources begin to emerge. There is a need, particularly with transportation and grid storage applications, where large amounts of energy need to be delivered or accepted quickly, within seconds or minutes. Although carbon based electrochemical capacitors possess the required power density, their relatively low energy density limits their usefulness for these applications. Instead, transition metal oxides that exhibit pseudocapacitance are very attractive. Pseudocapacitance occurs when reversible redox reactions occur at or near the surface of an electrode material and are fast enough so that the device's electrochemical features are those of a carbon-based capacitor, but with signicantly higher capacitances. It is important to recognize that pseudocapacitance in materials is a relatively new property, with the rst materials identied in the 1970's. Thus, both materials systems and electrochemical characteristics which lead to high energy density at high charge-discharge rates are still being identied. To date, transition metal oxides exhibit the widest range of materials with pseudocapacitive behavior. By selecting the proper transition metal oxide, utilizing the most effective electrode architecture, and analyzing the electrochemical behavior for pseudocapacitive behavior, such materials are expected to become the basis for electrochemical energy storage devices which offer high energy density at high rates.

There is an urgent global need for electrochemical energy storage that includes materials that can provide simultaneous high power and high energy density. One strategy to achieve this goal is with pseudocapacitive materials that take advantage of reversible surface or near-surface Faradaic reactions to store charge. This allows them to surpass the capacity limitations of electrical double-layer capacitors and the mass transfer limitations of batteries. The past decade has seen tremendous growth in the understanding of pseudocapacitance as well as materials that exhibit this phenomenon. The purpose of this Review is to examine the fundamental development of the concept of pseudocapacitance and how it came to prominence in electrochemical energy storage as well as to describe new classes of materials whose electrochemical energy storage behavior can be described as pseudocapacitive.

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Electrical energy storage plays an increasingly important role in modern society. Current energy storage methods are highly dependent on lithium-ion energy storage devices, and the expanded use of these technologies is likely to affect existing lithium reserves. The abundance of sodium makes Na-ion-based devices very attractive as an alternative, sustainable energy storage system. However, electrodes based on transition-metal oxides often show slow kinetics and poor cycling stability, limiting their use as Na-ion-based energy storage devices. The present paper details a new direction for electrode architectures for Na-ion storage. Using a simple hydrothermal process, we synthesized interpenetrating porous networks consisting of layer-structured V(2)O(5) nanowires and carbon nanotubes (CNTs). This type of architecture provides facile sodium insertion/extraction and fast electron transfer, enabling the fabrication of high-performance Na-ion pseudocapacitors with an organic electrolyte. Hybrid asymmetric capacitors incorporating the V(2)O(5)/CNT nanowire composites as the anode operated at a maximum voltage of 2.8 V and delivered a maximum energy of ∼40 Wh kg(-1), which is comparable to Li-ion-based asymmetric capacitors. The availability of capacitive storage based on Na-ion systems is an attractive, cost-effective alternative to Li-ion systems.

packaging, account for a large fraction of the total weight of the device, the use of thin electrodes results in a signifi cantly lower energy density than what could be attained using thicker electrodes. [ 3 ] Therefore, the development of thick electrodes for supercapacitors represents an important direction for making high-energy supercapacitors for practical applications.We recently developed a class of pseudocapacitive anode materials for asymmetric supercapacitors composed of interpenetrating networks of carbon nanotubes (CNTs) and V 2 O 5 nanowires. [ 16 ] The CNTs and nanowires were intimately intertwined into a hierarchically porous structure, enabling effective electrolyte access to the electrochemically active materials without limiting charge transport. Such composites exhibited high specifi c capacitance ( > 300 F g − 1 ) at high current density (1 A g − 1 ) in aqueous electrolyte. In this paper we report the fabrication of high energy density asymmetric supercapacitors containing thick-fi lm electrodes (over 100 μ m thick) of the CNT/V 2 O 5 nanowire composite in combination with an organic electrolyte, which allows for a higher initial cell potential. The excellent conductivity, high specifi c capacitance, and large voltage window of the CNT/V 2 O 5 nanocomposite enable the fabrication of devices with an energy density as high as 40 Wh kg − 1 at a power density of 210 W kg − 1 . Even at a high power density of 6 300 W kg − 1 , the device possesses an energy density of nearly 7.0 Wh kg − 1 . Moreover, the resulting devices exhibit excellent cycling stability. This work demonstrates that the nanowire composite approach is an effective strategy towards high-energy and high power density supercapacitors. Figure 1 A shows a representative scanning electron microscopy (SEM) image of a nanocomposite with 18 wt% of CNTs, demonstrating a continuous fi brous structure (Figure 1 A). The intertwined networks of the CNTs and nanowires exhibit an electrical conductivity of ≈ 3.0 S cm − 1 , which is 80 times higher than that of V 2 O 5 nanowires (0.037 S cm − 1 ). Figure 1 B is a transmission electron microscopy (TEM) image of a V 2 O 5 nanowire with a diameter of around 50 nm. The high-resolution TEM (HRTEM) image (inset) suggests the nanowire contains a layered crystalline structure; the small nanowire dimension allows effective Li + diffusion. Moreover, nitrogen sorption isotherms ( Figure S1, Supporting Information) and higher resolution SEM images of the etched composite fi lm (Figure 1 A, inset) show that the composite possesses a hierarchically porous structure; the presence of large pores enables rapid electrolyte transport while the small pores effectively increase the surface area available for electrochemical reactions. These small pores are responsible for the surface area of 125 m 2 g − 1 determined for the composite.An ideal electrical energy storage device provides both high energy and power density. [ 1 , 2 ] Supercapacitors exhibit signifi cantly higher power densities compared to batteries and ...

Capacitive energy storage offers several attractive properties compared to batteries, including higher power, faster charging, and a longer cycle life. A key limitation to this electrochemical energy‐storage approach is its low energy density and, for this reason, there is considerable interest in identifying pseudocapacitor materials where faradaic reactions are used to achieve greater charge storage. This paper reports on the electrochemical properties of Nb2O5 and establishes that crystalline phases of the material undergo fast faradaic reactions that lead to high specific capacitance in short charging times. In particular, the specific capacitance for the orthorhombic phase at infinite sweep rate reaches ≈400 F g−1, which exceeds that of birnessite MnO2 in nonaqueous electrolyte and is comparable to RuO2 at the same extrapolated rate. The specific capacitances of the orthorhombic and pseudohexagonal phases are much greater than that of the amorphous phase, suggesting that the faradaic reactions which lead to additional capacitive energy storage are associated with Li+ insertion along preferred crystallographic pathways. The ability for Nb2O5 to store charge at high rates despite its wide bandgap and low electronic conductivity is very different from what is observed with other transition metal oxides.

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